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Abraham Shanzer

Publications and source records attributed to Abraham Shanzer.

18 recordsLinked to original sources

A molecular keypad lock: a photochemical device capable of authorizing password entries.

This paper describes a new concept in the way information can be protected at the molecular scale. By harnessing the principles of molecular Boolean logic, we have designed a molecular device that mimics the operation of an electronic keypad lock, e.g., a common security circuit used for numerous applications, in which access to an object or data is to be restricted to a limited number of persons. What distinguishes this lock from a simple molecular logic gate is the fact that its output signals are dependent not only on the proper combination of the inputs but also on the correct order by which these inputs are introduced. In other words, one needs to know the exact passwords that open this lock. The different password entries are coded by a combination of two chemical and one optical input signals, which can activate, separately, blue or green fluorescence output channels from pyrene or fluorescein fluorophores. The information in each channel is a single-bit light output signal that can be used to authorize a user, to verify authentication of a product, or to initiate a higher process. This development not only opens the way for a new class of molecular decision-making devices but also adds a new dimension of protection to existing defense technologies, such as cryptography and steganography, previously achieved with molecules.

Journal Article↗

Divergent growth of coordination dendrimers on surfaces.

Divergent growth of surface-initiated dendritic nanostructures on gold surfaces in a highly controlled, stepwise manner is demonstrated, using metal-organic coordination as the binding motif. The repeat unit for dendrimer growth was a branched, C3-symmetrical ligand building block bearing three bis-hydroxamate groups. The surface initiation sites for dendrimer growth were obtained by the formation of a mixed monolayer comprising isolated bis-hydroxamate disulfide anchor ligands and octanethiol (OT) at very low anchor/OT ratios. Following functionalization of the surface with spaced anchors, alternate immersion in solutions of Zr4+ ions and the branched ligand afforded surface-confined dendrimers of increasing generation, where the number of generations is conveniently controlled by the number of coordination binding sequences. The heights of different generation dendrimers are in excellent agreement with values predicted by molecular models, as well as with thicknesses of branched multilayers prepared by the same procedure on full anchor monolayers. At higher generation numbers, gradual dendrimer overlap and coalescence are observed, eventually resulting in a continuous overlayer and a transition from 3D to 1D growth. A mechanism for the development of dendritic coordination nanostructures on surfaces is discussed.

Journal Article↗

A molecular full-adder and full-subtractor, an additional step toward a moleculator.

Over the past decade, there has been remarkable progress in the development of molecular logic and arithmetic systems, which has brought chemists closer to the realization of a molecular scale calculator (a Moleculator). This paper describes a significant step in this direction. By integrating past and new approaches for molecular logic reconfiguration, we were able to load advanced arithmetic calculations onto a single molecular species. Exchanging chemical inputs, monitoring at several wavelengths simultaneously, as well as using negative logic for the transmittance mode significantly increase the input and output information channels of the processing molecule. Changing the initial state of the processor is an additional approach used for altering the logical output of the device. Finally, introducing degeneracy to the chemical inputs or, alternatively, controlling their interactions to form identical chemical states minimizes the complexity of realizing three-bits addition and subtraction at the molecular scale. Consequently, using a commercially available fluorescein molecule, acid and base chemical inputs, and a simple UV-vis measurement setup, integration of a full-adder and, for the first time, a full-subtractor is now possible within individual molecules.

Anions↗

Branched coordination multilayers on gold.

A C3-symmetric tridentate hexahydroxamate ligand molecule was specially synthesized and used for coordination self-assembly of branched multilayers on Au surfaces precoated with a self-assembled monolayer (SAM) of ligand anchors. Layer-by-layer (LbL) growth of multilayers via metal-organic coordination using Zr4+ ions proceeds with high regularity, adding one molecular layer in each step, as shown by ellipsometry, wettability, UV-vis spectroscopy, and atomic force microscopy (AFM). The branched multilayer films display improved stiffness, as well as a unique defect self-repair capability, attributed to cross-linking in the layers and lateral expansion over defects during multilayer growth. Transmetalation, i.e., exposure of Zr4+-based assemblies to Hf4+ ions, was used to evaluate the cross-linking. Conductive atomic force microscopy (AFM) was used to probe the electrical properties of the multilayers, revealing excellent dielectric behavior. The special properties of the branched layers were emphasized by comparison with analogous multilayers prepared similarly using linear (tetrahydroxamate) ligand molecules. The process of defect annihilation by bridging over defective areas, attributed to lateral expansion via the excess bishydroxamate groups, was demonstrated by introduction of artificial defects in the anchor monolayer, followed by assembly of two layers of either the linear or the branched molecule. Analysis of selective binding of Au nanoparticles (NPs) to unblocked defects emphasized the superior repair mechanism in the branched layers with respect to the linear ones.

Journal Article↗

Sensitivity of transmission surface plasmon resonance (T-SPR) spectroscopy: self-assembled multilayers on evaporated gold island films.

The distance dependence of the localized surface plasmon (SP) extinction of discontinuous gold films is a crucial issue in the application of transmission surface plasmon resonance (T-SPR) spectroscopy to chemical and biological sensing. This derives from the usual sensing configuration, whereby an analyte binds to a selective receptor layer on the gold film at a certain distance from the metal surface. In the present work the distance sensitivity of T-SPR spectroscopy of 1.0-5.0 nm (nominal thickness) gold island films evaporated on silanized glass substrates is studied by using coordination-based self-assembled multilayers, offering thickness tuning in the range from approximately 1 to approximately 15 nm. The morphology, composition and optical properties of the Au/multilayer systems were studied at each step of multilayer construction. High-resolution scanning electron microscopy (HRSEM) showed no apparent change in the underlying Au islands, while atomic force microscopy (AFM) indicated flattening of the surface topography during multilayer construction. A regular growth mode of the organic layers was substantiated by X-ray photoelectron spectroscopy (XPS). Transmission UV-visible spectra showed an increase of the extinction and a red shift of the maximum of the SP band upon addition of organic layers, establishing the distance dependence of the Au SP absorbance. The distance sensitivity of T-SPR spectroscopy can be varied by using characteristic substrate parameters, that is, Au nominal thickness and annealing. In particular, effective sensitivity up to a distance of at least 15 nm is demonstrated with 5 nm annealed Au films. It is shown that intensity measurements, particularly in the plasmon intensity change (PIC) presentation, provide an alternative to the usually measured plasmon band position, offering good accuracy and the possibility of measuring at a single wavelength. The present distance sensitivity results provide the basis for further development of T-SPR transducers based on receptor-coated Au island films.

Journal Article↗

Fluorescein as a model molecular calculator with reset capability.

The evolution of molecules capable of performing boolean operations has gone a long way since the inception of the first molecular AND logic gate, followed by other logic functions, such as XOR and INHIBIT, and has reached the stage where these tiny processors execute arithmetic calculations. Molecular logic gates that process a variety of chemical inputs can now be loaded with arrays of logic functions, enabling even a single molecular species to execute distinct algebraic operations: addition and subtraction. However, unlike electronic or optical signals, the accumulation of chemical inputs prevents chemical arithmetic systems from resetting. Consequently, a set of solutions is required to complete even the simplest arithmetic cycle. It has been suggested that these limitations can be overcome by washing off the input signals from solid supports. An alternative approach, which does not require solvent exchange or incorporation of bulk surfaces, is to reset the arithmetic system chemically. Ultimately, this is how some biological systems regenerate. Here we report a highly efficient and exceptionally simple molecular arithmetic system based on a plain fluorescein dye, capable of performing a full scale of elementary addition and subtraction algebraic operations. This system can be reset following each separate arithmetic step. The ability to selectively eradicate chemical inputs brings us closer to the realization of chemical computation.

Computers, Molecular↗

Preparative manipulation of gold nanoparticles by reversible binding to a polymeric solid support.

A preparative scheme is presented for controlled modification of gold nanoparticles (NPs) by using reversible binding to a polymeric solid support through boronic acid chemistry. Octanethiol-capped Au NPs were bound to a boronic acid functionalized resin by custom-synthesized bifunctional linker molecules. The NPs were chemically released from the resin to the solution, with one (or a few) linker molecules embedded in their capping layer. This was confirmed by rebinding the linker-derivatized NPs to a boronic resin, exploiting the reversibility of the boronic acid/diol chemistry. The same scheme was employed to demonstrate a new method for affinity separation of NPs by means of a solid-phase reaction. The use of boronic acid provides versatility and chemical reversibility, while the polymeric solid support affords the separation and preparative aspects. The method presented here may be useful in various facets of NP handling, manipulation, and separation.

Journal Article↗

Ferrioxamine B analogues: targeting the FoxA uptake system in the pathogenic Yersinia enterocolitica.

A series of ferrioxamine B analogues that target the bacterium Yersinia enterocolitica were prepared. These iron carriers are composed of three hydroxamate-containing monomeric units. Two identical monomers consist of N-hydroxy-3-aminopropionic acid coupled with beta-alanine, and a third unit at the amino terminal is composed of N-hydroxy-3-aminopropionic acid and one of the following amino acids: beta-alanine (1a), phenylalanine (1b), cyclohexylalanine (1c), or glycine (1d). Thermodynamic results for representatives of the analogues have shown a strong destabilization (3-4 orders of magnitude) of the ferric complexes with respect to ferrioxamine B, probably due to shorter spacers and a more strained structure around the metal center. No significant effect of the variations at the N-terminal has been observed on the stability of the ferric complexes. By contrast, using in vivo radioactive uptake experiments, we have found that these modifications have a substantial effect on the mechanism of iron(III) uptake in the pathogenic bacteria Yersinia enterocolitica. Analogues 1a and 1d were utilized by the ferrioxamine B uptake system (FoxA), while 1b and 1c either used different uptake systems or were transported to the microbial cell nonspecifically by diffusion via the cell membrane. Transport via the FoxA system was also confirmed by uptake experiments with the FoxA deficient strain of Yersinia enterocolitica. A fluorescent marker, attached to 1a in a way that did not interfere with its biological activity, provided additional means to monitor the uptake mechanism by fluorescence techniques. Of particular interest is the observation that 1a was utilized by the uptake system of ferrioxamine B in Yersinia enterocolitica (FoxA) but failed to use the ferrioxamine uptake route in Pseudomonas putida. Here, we present a case in which biomimetic siderophore analogues deliberately designed for a particular bacterium can distinguish between related uptake systems of different microorganisms.

Bacterial Outer Membrane Proteins↗

Chemical input multiplicity facilitates arithmetical processing.

We describe the design and function of a molecular logic system, by which a combinatorial recognition of the input signals is utilized to efficiently process chemically encoded information. Each chemical input can target simultaneously multiple domains on the same molecular platform, resulting in a unique combination of chemical states, each with its characteristic fluorescence output. Simple alteration of the input reagents changes the emitted logic pattern and enables it to perform different algebraic operations between two bits, solely in the fluorescence mode. This system exhibits parallelism in both its chemical inputs and light outputs.

Journal Article↗

Layer-by-layer assembly of ordinary and composite coordination multilayers.

Coordination self-assembly of bishydroxamate-based metal-organic multilayers on gold employing a layer-by-layer (LbL) approach was investigated. It is shown that the solution chemistry of the participating metal ion has a marked influence on the composition and properties of the multilayers. Use of Ce4+ and particularly zirconium(IV) acetylacetonate (Zr(acac)4) solutions in the ion-binding step of multilayer construction leads to multilayers with a near-stoichiometric metal ion-to-ligand ratio, suggesting a structure close to that predicted by a simple coordination self-assembly scheme. On the other hand use of a ZrCl4 solution as the source of metal ions in the multilayer construction leads to a multilayer with greater thickness and a large excess of Zr(IV), evenly distributed between the organic layers. In the latter case, a ratio of ca. 1:2 between the excess Zr and oxygen, as well as long-term Zr4+ binding experiments showing deposition of ZrO2, suggest the formation of a zirconia-type nanophase between the bishydroxamate organic repeat units during multilayer self-assembly. Hence, while the multilayer prepared using Zr(acac)4 solution appears to represent a "true" coordination-based structure, the one prepared using ZrCl4 is best described as a composite organic-ceramic multilayer. Composite multilayers prepared in this way display different properties from those of the stoichiometric ones, such as improved dielectric behavior and higher stiffness. Even greater mechanical stability is obtained with multilayers constructed using alternate binding of ZrCl4 and Ce4+. The concept of LbL formation of coordination-based composite organic-ceramic structures may be useful in obtaining nanometer-scale structures with tunable properties.

Cesium↗

Stable room-temperature molecular negative differential resistance based on molecule-electrode interface chemistry.

We show reproducible, stable negative differential resistance (NDR) at room temperature in molecule-controlled, solvent-free devices, based on reversible changes in molecule-electrode interface properties. The active component is the cyclic disulfide end of a series of molecules adsorbed onto mercury. As this active component is reduced, the Hg-molecule contact is broken, and an insulating barrier at the molecule-electrode interface is formed. Therefore, the alignment of the molecular energy levels, relative to the Fermi levels of the electrodes, is changed. This effect results in a decrease in the current with voltage increase as the reduction process progresses, leading to the so-called NDR behavior. The effect is reproducible and repeatable over more than 50 scans without any reduction in the current. The stability of the system, which is in the "solid state" except for the Hg, is due to the molecular design where long alkyl chains keep the molecules aligned with respect to the Hg electrode, even when they are not bound to it any longer.

Journal Article↗

Direct photo-induced DNA strand scission by a ruthenium bipyridyl complex.

Irradiation of plasmid DNA in the presence of Ru(II)-2, a modified tris(2,2'-bipyridyl)Ru(II) complex, in which two hydroxamic acid groups are attached to one of the three bipyridyl ligands, results in total fragmentation of the DNA. The photo-chemical reaction products were analyzed by gel electrophoresis, which revealed complete fragmentation. Further evidence for the complete degradation of the DNA was obtained by imaging the pre- and post-treated plasmid DNA using atomic force microscopy (AFM). A mechanism for the reaction is proposed. It initially involves the photo-chemical generation of Ru(III) ions and superoxide radicals, as corroborated by absorbance difference spectroscopy and electron paramagnetic resonance (EPR). Consequently, Ru(III) preferentially oxidizes guanine, liberating superoxide radicals that yield OH radicals. The OH radicals were identified by observing the spectral change at 532 nm of a 5'-dAdG substrate forming a colored adduct with thiobarbituric acid. These radicals are associated with the major non-specific damage exerted to DNA.

2,2'-Dipyridyl↗

Application of the empirical force field to macrocyclic ion carriers, siderophores, and biomimetic analogs.

The empirical force field (EFF), developed by Prof. Lifson, was applied to the study of macrocyclic alkali ion carriers and to di- and tripodal and open chain siderophores and synthetic biomimetic molecules binding transition metals. The highly symmetric nature of these structures facilitated a favorable coordination geometry of the ligating groups about the metal, which helped organize the entire molecule into a fairly rigid structure. In our combined experimental-theoretical approach, EFF calculations were used to help predict likely candidates to synthesize, and provided a wealth of structural data to complement what we learned from the spectroscopic measurements, while feedback from these measurements allowed us to continue improving the EFF itself. The simple, highly modular design of the biomimetic analogs allowed rapid synthesis and systematic examination of a large number of related structures, as well as facilitating an efficient, piecewise conformational scanning for the theoretical calculations. In the early years, we focused on macrocyclic polylactones and lactams binding monovalent alkali ions, particularly the natural products enniatin and valinomycin, including inside a crystal lattice. Later we switched to bi- and tridentate siderophores, natural microbial iron carriers, and synthetic biomimetic analogs-in particular, of enterobactin, ferrichrome, and ferrioxamine B. Over the years a large number of biomimetic siderophores have been prepared, some active in a broad range of microorganisms while others are highly species specific. The results of this work have broad applications in many areas, including the design of novel drugs and antimicrobial agents, helical polymeric structures, and polynuclear metal complexes.

Ion Transport↗

Synthesis and evaluation of iron chelators with masked hydrophilic moieties.

Synthetic iron chelators based on the natural siderophore ferrichrome have previously been shown to bind Fe(III) with high affinity (pKf > 27) and have shown no toxicity to mammalian cell cultures in vitro. A new class of lipophilic ferrichrome analogues carrying acetoxymethyl ester moieties has been synthesized. We have shown that these molecules penetrate rapidly through cell membranes and turn highly hydrophilic while inside the cells, upon esterase mediated hydrolysis of the lipophilic termini. The intracellular retention was visualized by labeling these analogues with a fluorescent naphthalic diimide probe. The prohydrophilic iron chelators have been shown to inhibit the metal-catalyzed intracellular formation of reactive oxygen species with high effectivity, and preliminary results suggest these molecules to be potent antimalarial agents.

Animals↗

Bidentate ligation of heme analogues; novel biomimetics of peroxidase active site.

The multifunctional nature of proteins that have iron-heme cofactors with noncovalent histidine linkage to the protein is controlled by the heme environment. Previous studies of these active-site structures show that the primary difference is the length of the iron-proximal histidine bond, which can be controlled by the degree of H-bonding to this histidine. Great efforts to mimic these functions with synthetic analogues have been made for more than two decades. The peroxidase models resulted in several catalytic systems capable of a large range of oxidative transformations. Most of these model systems modified the porphyrin ring covalently by directly binding auxiliary elements that control and facilitate reactivity; for example, electron-donating or -withdrawing substituents. A biomimetic approach to enzyme mimicking would have taken a different route, by attempting to keep the porphyrin ring system unaltered, as close as possible to its native form, and introducing all modifications at or close to the axial coordination sites. Such a model system would be less demanding synthetically, would make it easy to study the effect of a single structural modification, and might even provide a way to probe effects resulting from porphyrin exchange. We introduce here an alternative model system based on these principles. It consists of a two component system: a bis-imidazolyl ligand and an iron-porphyrin (readily substituted by a hemin). All modifications were introduced only to the ligand that engulfs the porphyrin and binds to the iron's fifth and sixth coordination sites. We describe the design, synthesis, and characterization of nine different model compounds with increased complexity. The primary tool for characterizing the environment of each complex Fe(III) center was the Extended X-ray Absorption Fine Structure (EXAFS) measurements, supported by UV/Vis, IR, and NMR spectroscopy and by molecular modeling. Introduction of asymmetry, by attaching different imidazoles as head groups, led to the formation of two axial bonds of different length. Addition of H-bonds to one of the imidazoles in an advanced model increased this differentiation and expanded the porphyrin ring. These complexes were found to be almost identical in structure to peroxidase active sites. Similarly to the peroxidases and other synthetic models, these compounds stabilize the green, compound I-like intermediate, and catalyze the oxidation of organic substrates.

Binding Sites↗

Molecular engineering of semiconductor surfaces and devices.

Grafting organic molecules onto solid surfaces can transfer molecular properties to the solid. We describe how modifications of semiconductor or metal surfaces by molecules with systematically varying properties can lead to corresponding trends in the (electronic) properties of the resulting hybrid (molecule + solid) materials and devices made with them. Examples include molecule-controlled diodes and sensors, where the electrons need not to go through the molecules (action at a distance), suggesting a new approach to molecule-based electronics.

Journal Article↗